US4988607A - High speed photopolymerizable element with initiator in a topcoat - Google Patents

High speed photopolymerizable element with initiator in a topcoat Download PDF

Info

Publication number
US4988607A
US4988607A US07/357,908 US35790889A US4988607A US 4988607 A US4988607 A US 4988607A US 35790889 A US35790889 A US 35790889A US 4988607 A US4988607 A US 4988607A
Authority
US
United States
Prior art keywords
carbon atoms
assembly
recited
photoinitiator
aromatic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US07/357,908
Other languages
English (en)
Inventor
Mohammad Z. Ali
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
3M Co
Original Assignee
Minnesota Mining and Manufacturing Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Minnesota Mining and Manufacturing Co filed Critical Minnesota Mining and Manufacturing Co
Priority to US07/357,908 priority Critical patent/US4988607A/en
Assigned to MINNESOTA MINING AND MANUFACTURING COMPANY, A CORP. OF DELAWARE reassignment MINNESOTA MINING AND MANUFACTURING COMPANY, A CORP. OF DELAWARE ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: ALI, MOHAMMAD Z.
Priority to CA002015852A priority patent/CA2015852A1/fr
Priority to EP90305728A priority patent/EP0403096B1/fr
Priority to DE69028044T priority patent/DE69028044T2/de
Priority to KR1019900007742A priority patent/KR910020499A/ko
Priority to JP2139563A priority patent/JPH0329948A/ja
Application granted granted Critical
Publication of US4988607A publication Critical patent/US4988607A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/095—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having more than one photosensitive layer
    • G03F7/0955—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having more than one photosensitive layer one of the photosensitive systems comprising a non-macromolecular photopolymerisable compound having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/162—Protective or antiabrasion layer

Definitions

  • This invention relates to photopolymerizable compositions, particularly to photopolymerizable printing plate compositions, and more particularly to printing plate compositions which are highly sensitive to visible light and have good shelf-life.
  • Photopolymerizable compositions have been used in photosensitive elements, such as printing plates, for a number of years. Most representative of the prior art are compositions disclosed in U.S. Pat. Nos. 3,218,167 and 3,887,450. These compositions are relatively slow, however, and must be exposed in the absence of oxygen. Radiation sensitive elements which are oxygen insensitive have been produced by overcoating the elements with an oxygen barrier layer as disclosed in U.S. Pat No. 3,895,949. These elements nevertheless remain relatively slow and such compositions have been satisfactory only where contact printing of the plate and relatively long time exposures can be tolerated.
  • Photopolymerizable compositions with higher sensitivity are required for applications such as projection printing plates and laser addressable printing plates.
  • high speed is essential to keep the exposure time short and also to be able to use low intensity lasers, which are of low cost and are more reliable than the high intensity lasers.
  • various efforts have been carried out to improve the sensitivity of photopolymerizable compositions.
  • thermal polymerization inhibitors To improve the storage stability of photopolymerizable compositions, several thermal polymerization inhibitors have been used. These thermal polymerization inhibitors are well known in the art and are described in many patents and literature, such as, U.S. Pat. Nos. 4,168,982; 4,361,640; 4,198,242; 4,148,658. Although the thermal polymerization inhibitors increase the storage stability of the photopolymerizable compositions, one major drawback of using many of these compounds is the decreased photosensitivity imparted by these compounds. This decreased sensitivity is a major hindrance to the potential applications requiring high sensitivity, such as projection exposure imaging and laser imaging.
  • U.S. Pat. No. 3,458,311 teaches the utility of overcoating the photopolymerizable composition with an oxygen barrier top coat layer.
  • a typical oxygen barrier top coat layer is polyvinyl alcohol or gelatin and the layer is usually coated from aqueous solutions on top of the polymerizable light sensitive layer. After exposure, these barrier layers are removed by washing with aqueous solutions, during or before development.
  • the oxygen barrier layer may contain other additives, such as polyvinlypyrrolidone/vinyl acetate copolymer, discrete inert particles or beads such as polytrimethylolpropane trimethacrylate (U.S. Pat. No. 4,599,299).
  • Strippable oxygen barrier layers are also known in the prior art.
  • U.S. Pat. Nos. 4,454,218, 3,652,275, and 4,148,658 teach lamination of a polyethylene terephthalate film support to the photopolymerizable layer. After exposure the cover sheet is removed.
  • Trialkylamines, arylalkylamines including p-substituted-N-disubstituted anilines are well known in the prior art. These compounds are known to act as photopolymerization accelerators.
  • U.S. Pat. No. 4,366,228 lists p-substituted-N-disubstituted anilines as photoseveral activators with ketocoumarin compounds. These compounds also act as activators with other keto compounds, such as thioxanthones, fluorenones ("Polymerization of Surface Coatings," C. G. Roffey, Wiley Interscience Publication, 1982), and 1,2-dicarbonyl compounds (U.S. Pat. No. 3,756,827 Re 28,789; 4,072,424).
  • thermal polymerization inhibitors known in the art are p-methoxyphenol, 2,6-di-tert-butyl-p-cresol, hydroquinone, alkyl and aryl substituted hydroquinones, tert-butyl-catechol, pyrogallol, ⁇ -napthol, p-benzoquinone, p-toluquinone, chloranil, nitrobenzene, dinitrobenzene, dicyclopenta-dienyliron, thiazine dyes, e.g.
  • the invention relates to the provision of a highly sensitive photopolymerizable layer assembly with improved storage properties.
  • the invention also relates to providing increased speed to a photopolymerizable layer assembly comprising an ethylenically unsaturated polymerizable compound, and a free radical producing photoinitiator composition.
  • a further aspect of the invention is to provide photosensitive printing plates which have high exposure speed while exhibiting good shelf-life, and which are developable with aqueous alkali solutions.
  • the present invention therefore, provides a layer assembly comprising a substrate having at least two layers over one surface of the substrate.
  • the lower layer i.e., closest to the substrate
  • the top layer is an oxygen barrier overcoat, which contains a photoinitiator composition soluble in the barrier layer.
  • photoinitiators A wide range of compounds known in the art as photoinitiators are suitable, but preferred compounds for this invention are diaryliodonium salts, trihalomethyl-s-triazines and other halogenated hydrocarbons (e.g., hydrocarbon groups having photolabile halogens) known in the art to produce free radical polymerization.
  • diaryliodonium salts e.g., trihalomethyl-s-triazines
  • other halogenated hydrocarbons e.g., hydrocarbon groups having photolabile halogens
  • incorporation of photoinitiator in the oxygen barrier layer provides a higher concentration of photoinitiator near the surface of the photopolymerizable composition and this helps in overcoming the detrimental effect of oxygen inhibition (concentration of oxygen is very likely to be higher, near the surface of the photopolymerizable composition).
  • an improved photo-polymerizable layer assembly comprises at least two layers on one surface of a substrate. There is a lower layer adjacent to the substrate and a top layer between the lower layer and the atmosphere.
  • the lower layer comprises
  • imaging addenda e.g., solvents, antistatic agents, coating aids, dyes, stabilizers, fillers, etc.
  • the top layer the oxygen barrier layer, comprises
  • a barrier polymeric binder chosen from those known in the art as providing an oxygen barrier (e.g., polyvinyl alcohol, gelatin, polyvinylpyrolidone)
  • the lower layer may contain a compound selected from p-substituted-N- disubstituted anilines.
  • the lower layer contains between 0 and 80 mole percent and the top layer contains between 100 and 20 mole percent of photoinitiator.
  • the lower layer contains 50 to 70 mole % and the top layer 50 to 30 mole % of photoinitiator in the assembly (at least the two coated layers).
  • the total photoinitiator present in the assembly is between 1 and 20 weight % of the dried weight of the lower and top layers combined weight.
  • the amount of p-substituted-N-disubstituted aniline in the lower layer is between 0.2 and 10 weight % of the dry weight of the layer.
  • the dry coating weight of the lower layer is between 0.3 g/m 2 and 9 g/m 2 , and preferably between 0.5 g/m 2 and 3.3 g/m 2 , and of the top layer between 0.5 g/m 2 and 3.3 g/m 2 .
  • the sensitizer may be present only in the lower layer or may be divided between the lower and top layers in various ratios to the photoinitiators present. Because the top layer is removed during development of the plate, placing all of the sensitizer in the top layer (in the case when all the photoinitiator is in that layer) gives the advantage that all or at least most of the colored material is removed from the developed plate.
  • the choice of a different photoinitiator in the top layer from that in the lower layer may be based on the better compatibility (e.g., solubility or dispersibility) of some photoinitiators with the polymers of one layer or the other.
  • the photoinitator is chosen from compounds which generate free radicals upon exposure to actinic radiation, in the presence of a sensitizer if necessary.
  • free radical photoinitiators are materials known in the art, such as "Free-Radical Chemistry", D. C. Nonhebel and J. C. Walton, University Press (1974).
  • Particularly suitable free radical photoinitiators can be selected from many classes of organic compounds including, for example, organic peroxides, azo compounds, aromatic diazonium salts, aromatic iodonium salts, aromatic sulfonium salts, aromatic phosphonium salts, quinone, benzophenones, nitroso compounds, acyl halides, aryl halides, hydroazones, mercapto compounds, pyrilium compounds, triarylimidazoles, biimidazoles, haloalkyltriazines, etc. These materials, generally, must have photosensitizers therewith to form a photoinitiator system. Photosensitizers are well known in the art.
  • sensitizers therein.
  • Another good reference to photoinitiator systems is "Light Sensitive Systems,” J. Kosar, 1965, J. Wiley and Sons, Inc. especially Chapter 5.
  • Particularly preferred sensitizers for iodonium salts and halogenated triazines are disclosed in U.S. Pat. Application Ser. No. 275,516 filed Nov. 23, 1988.
  • Preferred photoinitiator compounds are aromatic iodonium salts, trichloromethyl-s-triazines, and other halogenated hydrocarbon compounds.
  • Aromatic iodonium salts which are suitable as photoinitiators and which also may be incorporated into the oxygen barrier layer may include compounds from U.S. Pat. No. 4,250,053 that are soluble or dispersible in the said oxygen barrier layer.
  • Ar 1 and Ar 2 are aromatic groups having from 4 to 20 carbon atoms and are preferably selected from phenyl, naphthyl, thienyl, furanyl and pyrazolyl groups, W is selected from a single bond, ⁇ O, ⁇ S, ⁇ S ⁇ O, ⁇ C ⁇ O, ##STR2## ⁇ N--R 13 , and ⁇ CR 11 R 12 where R 13 is aryl of 6 to 20 carbon atoms, acyl of 2 to 20 carbon atoms, in which R 11 and R 12 are selected from hydrogen, alkyl groups of 1 to 4 carbon atoms, Q is any anion, e.g., an acid anion, preferably selected from tetraborate, and halogen-containing complex anions, and more preferably selected from hexafluorophosphate, hexafluoroarsenate, and hexafluoroantimonate.
  • W is selected from a single bond, ⁇ O, ⁇ S, ⁇ S ⁇
  • Preferred iodonium compounds are diphenyl iodonium hexa-fluorophosphate, diphenyliodonium chloride, p-methoxy diphenyl iodonium acetate.
  • Halogenated hydrocarbon compounds including triazines which are valuable as photoinitiators and which also may be incorporated into the oxygen barrier layer include those compounds from U.S. Pat. No. 3,617,288 and 4,505,793 which are soluble in the said oxygen barrier layer.
  • Preferred compounds are halogenated triazines of the general formula: ##STR3## wherein,
  • X is a halogen atom (preferably chlorine or bromine),
  • Y is --CX 3 , --NH 2 , --NHR 15 , --NP 15 2 , or --OR 15 , wherein R 15 is an alkyl group of 1 to 4 carbon atoms or an aryl group containing 6 to 10 carbon atoms, and
  • R 16 is --CX 3 , an alkyl group of 1 to 12 carbon atoms, an aryl group of 6 to 12 carbon atoms, an alkenyl group of 2 to 12 carbon atoms, or an aralkenyl group containing from 8 to 20 carbon atoms.
  • the top layer is an oxygen barrier layer chosen to be substantially impermeable to oxygen, water-permeable and comprising said barrier polymeric binder selected from macromolecular organic polymers or polymer mixtures that are soluble between about 20° C. and 50° C. in water or in a mixture of water and a water-miscible organic solvent containing at least 50% by volume of water.
  • said barrier polymeric binder selected from macromolecular organic polymers or polymer mixtures that are soluble between about 20° C. and 50° C. in water or in a mixture of water and a water-miscible organic solvent containing at least 50% by volume of water.
  • Useful macromolecular organic polymers having the characteristics given above are given in U.S. Pat. No. 3,458,311 and include polyvinyl alcohol and its partial esters, ethers and acetals that contain a substantial amount of unsubstituted vinyl alcohol units so that they have the requisite solubility in water. Suitable polymers include 88% to 99% hydrolyzed polyvinyl acetate. Other useful polymers include gelatin, gum arabic, copolymers of vinyl ethers and maleic anhydride , polyvinyl pyrrolidones, high molecular weight, water-soluble polymers of ethylene oxide having an average molecular weight of about 100,000 to 3,000,000 or more, and mixtures of these polymers.
  • Preferred oxygen barrier layer polymers are polyvinylalcohol, carboxymethylcellulose or mixtures thereof.
  • the choice of photoinitiator for compatibility with the barrier layer may be different from that chosen for the lower photopolymerizable layer.
  • the free radically polymerizable compounds at least one of which is used in the lower layer are compounds containing at least one ethylenically unsaturated double bond and may be a monomer, a prepolymer, i.e. a dimer, a trimer, and other oligomers, a mixture thereof, or a copolymer. Suitable examples are the preferred monomers listed in U.S. Pat. Nos. 4,228,232 and 4,476,215. If the free radically polymerizable compound is a monomer, it has preferably 2 to 4 ethylenically unsaturated groups such as acryloyl, methacryloyl, vinyl and allyl.
  • acrylic esters of low molecular weight polyols such as trimethylolpropanetriacrylate, pentaerythritol tetraacrylate, and triacrylate, etc.
  • these monomers have a molecular weight of less then 2,000 and more preferrably less then 1,000.
  • Other suitable free radical polymerizable monomers useful in the compositions of the invention are well known and listed in many patents, e.g., U.S. Pat. No. 3,895,949 and 4,037,021.
  • Preferred monomers are the polyacrylates and polymethacrylate esters of alkanepolyols, e.g., pentaerythritol tetraacrylate, tris(2-acryloxyethyl)-isocyanurate,2-acetoxyethyl methacrylate, tetrahydrofurfurylmethacrylate, 1-aza-5-acryloxymethyl-3,7-dioxabicyclo[ 3,0,0]octane (ADOZ), bis[4-(2-acryloxyethyl)phenyl]dimethylmethane,diacetone acrylamide, acrylamidoethyl methacrylate.
  • alkanepolyols e.g., pentaerythritol tetraacrylate, tris(2-acryloxyethyl)-isocyanurate,2-acetoxyethyl methacrylate, tetrahydrofurfurylmethacrylate, 1-
  • Free radical polymerizable oligomers with pendant carboxyl groups are known in the art. These can be advantageous in providing dispersibility in aqueous alkali developers. Some representative examples are U.S. Pat. Nos. 3,887,450, 3,448,089, 4,162,274, 4,228,232 and U.S. Pat. Application Ser. No. 151,879 filed Feb. 3, 1988. The most preferred oligomers are found in the latter two references. Controlling the number of acid groups on the oligomer is an effective way of controlling the bondability of the composition to the substrate after photoinitiated reaction. With increasing acid concentration, the composition is more easily removed in development. A wide range of acid contents can be used depending on the performance characteristics desired in the final product.
  • a film-forming polymeric binder may be added to the composition of the lower layer and in most cases it is advantageous to do so. Indeed where the free radically polymerizable compound is tacky or free flowing it is often imperative to add a polymeric binder.
  • a wide range of suitable binders is known in the art for photopolymerization compositions and suitable examples may be found in U.S. Pat. Nos.
  • 4,228,232 and 4,476,215 including polyvinylacetals, polyvinylbutyral, poly(vinyl methylether), polyvinylalcohol, hydroxyalkylcellulose, polyamides, polyvinylacetate, polyvinylacetate-polyvinylchloride copolymers, polyethyleneoxides, polyacrylates, and polymethacrylates.
  • Suitable sensitizers include compounds in the following categories: ketones, coumarin dyes (e.g., ketocoumarins), xanthene dyes, 3H-xanthen-3-one dyes, acridine dyes, thiazole dyes, thiazine dyes, oxazine dyes, azine dyes, aminoketone dyes, methines and polymethines, porphyrins, aromatic polycyclic hydrocarbons, p-substituted aminostyryl ketone compounds, aminotriaryl methanes, merocyanines, squarylium dyes and pyridinium dyes.
  • ketones coumarin dyes (e.g., ketocoumarins), xanthene dyes, 3H-xanthen-3-one dyes, acridine dyes, thiazole dyes, thiazine dyes, oxazine dyes, azine dyes, aminoketone dyes,
  • Ketones e.g., monoketones or alpha-diketones
  • ketocoumarins aminoarylketones
  • p substituted aminostyryl ketone compounds merocyanines
  • aromatic polycyclic hydrocarbons are preferred sensitizers.
  • sensitizers having an extinction coefficient below about 1000, more preferably below about 100, at the desired wavelength of irradiation for photopolymerization.
  • ketone sensitizers has the formula:
  • X is CO or CR 1 R 2 , where R 1 and R 2 can be the same or different, and can be hydrogen, alkyl, alkaryl or aralkyl, b is zero or 1, and A and B can be the same or different and can be substituted (having one or more non-interfering substitutents) or unsubstituted aryl, alkyl, alkaryl, or aralkyl groups, or together A and B can form a cyclic structure which can be a substituted or unsubstituted cycloaliphatic, aromatic, heteroaromatic or fused aromatic ring.
  • Suitable diketones include araklydiketones such as anthraquinone, phenanthrenequinone, o-, m- and p-diacetylbenzene, 1,3-,1,4-, 1,5-, 1,6- 1,7- and 1,8-diacetylnaphthalene, 1,5-, 1,8- and 9,10-diacetylanthracene, and the like.
  • araklydiketones such as anthraquinone, phenanthrenequinone, o-, m- and p-diacetylbenzene, 1,3-,1,4-, 1,5-, 1,6- 1,7- and 1,8-diacetylnaphthalene, 1,5-, 1,8- and 9,10-diacetylanthracene, and the like.
  • Suitable beta-diketones include 2,3-butanedione, 2,3-pentanedione, 2,3-hexanedione, 3,4-hexanedione, 2,3-heptanedione, 3,4-heptanedione, 2,3-octanedione, 4,5-octanedione, benzil 2,2'-3,3,and 4,4,-dihydroxybenzil, furil, di-3,3,-indolylethan 2,3-bornanedione (camphorquinone), biacetyl, 1,2-cyclohexanedione, 1,2-naphthoquinone, acenaphthaquinone, and the like.
  • ketocoumarins and p-substituted aminostyryl ketone compounds are listed in Table II in copending U.S. Pat. Application Ser. No. 34,065.
  • Preferred merocyanine dyes are listed in U.S. Pat. No. 3,729,313.
  • compositions of the invention can be exposed and thereby cured using a variety of methods. It is convenient to employ light sources that emit ultraviolet or visible light such as quartz halogen lamps, tungsten-halogen lamps, mercury lamps, Xenon and Mercury/Xenon lamps, plasma arcs, light emitting diodes and lasers. In general, heat will accelerate cure.
  • light sources that emit ultraviolet or visible light such as quartz halogen lamps, tungsten-halogen lamps, mercury lamps, Xenon and Mercury/Xenon lamps, plasma arcs, light emitting diodes and lasers. In general, heat will accelerate cure.
  • p-substituted-N-disubstituted anilines which may be added to the lower layer to further improve the shelf-life are selected from those with the general structure (1) ##STR4## wherein,
  • R 1 and R 2 are the same or different and are each alkyl containing from 1 to 12 carbon atoms, or together with a nitrogen atom they form one or more hetrocyclic rings having from 5 to 10 nuclear atoms,
  • R 3 is the group --COOR 4 or the group --(C ⁇ O)--R 5 ,
  • R 4 is H, alkyl, hydroxyalkyl, carboxyyalkyl, aralkyl, or aryl, where alkyl has from 1 to 15 carbon atoms, and aryl is phenyl or naphthyl,
  • R 5 is H, alkyl group containing from 1 to 4 carbon atoms, phenyl group, or naphthyl group
  • R 6 , R 7 , R 8 , R 9 are independently H, alkyl group, hydroxy, alkoxy group, halogen, cyano, or R 6 and R 7 together or R 8 and R 9 together may independently form cyclic structures containing up to 8 ring atoms.
  • the photopolymerizable composition of the invention containing the above-described ethylenic compound and photosensitizer-photoinitiator system may further contain, if desired, known additives such as thermal polymerization inhibitors, plasticizers, coloring agents, and surface lubricants (U.S. Pat. No. 4,228,232).
  • Substrates for the layer assembly may be chosen from a wide variety of materials according to the end purpose of the photopolymerizable layer assembly. Thus for printing plates grained and anodized aluminum sheet may be used; for color proofing materials clear polymer substrates may be used. In general substrates chosen to be nonpermeable to oxygen are preferred such as metals, polymers, and treated papers.
  • the polymerizable composition of the present invention are particularly useful in presensitized printing plate, and color proofing systems.
  • the high speed of the compositions and yet high storage stability are very desirable for commercialization of projection exposure imaging systems and particularly imaging systems based on exposure by laser scanning techniques.
  • This example demonstrates the advantage of photoinitiator in the top coat in the presence of different sensitizers and stabilizers.
  • the carboxyl substituted urethane oligomer is similar to the oligomer P-II disclosed in U.S. Pat. No. 4,228,232, and was made by the same preparative route.
  • the oligomer in this Example is characterized as having a molecular weight of 4300, a carboxy equivalent weight of 1100, and an acrylate equivalent weight of 700.
  • the amount of triethylamine was just sufficient to neutralize the carboxy groups of the urethane oligomer.
  • the exposed plates were developed with an aqueous solution of 4% n-propanol, 2% sodium metasilicate and 0.06% Dowfax® 2Al surfactant (Dow Chemical Company).
  • Table 1 shows the polymer retained according to the number of steps after exposure and development.
  • the step values (solid) indicate the exposure level at which the developed image density can no longer be differentiated from the background and is believed to be cured to the desired level.
  • Absolute sensitivity thresholds of some of the samples were also measured by exposing with a monochromatic light source of wavelength 488 nm. Table 2 gives these results.
  • the lamp output was measured by a radiometer.
  • the coated plates were covered with black paper and kept in an oven set at 140° F. (60° C.) for 3 days. After allowing to cool to room temperature, the samples were exposed and developed as above.
  • samples 1 and 2 show the results obtained with state of the art topcoat and no stabilizer.
  • Samples 3 to 5 demonstrate that antioxidants commonly used in the art to increase speed or to stabilize these materials, in fact produce a worsening of the stability of our materials.
  • samples 6 to 9 using p-substituted aryldialkylamines give some improvement.
  • the use of Ph 2 I + PF 6 - in the topcoat in samples 10 to 12 shows improvement over the use of a stabilizer.
  • samples 13 and 14 the use of such a topcoat with a stabilizer is shown to give a dramatic improvement in stability with increase in speed.
  • This example demonstrates the effect of various levels of partitioning of the photoinitiator between a main layer and a topcoat.
  • Example 2 To 5 g of the stock solution in Example 1 was added 6 mg of sensitizer I of that example.
  • Bilayer coatings were made on grained and anodized aluminum as described in Example 1 but with the photoinitiator additions to the two layers as indicated in Table 3. Testing was also carried out as in that example.

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Polymerisation Methods In General (AREA)
  • Paints Or Removers (AREA)
US07/357,908 1989-05-30 1989-05-30 High speed photopolymerizable element with initiator in a topcoat Expired - Lifetime US4988607A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
US07/357,908 US4988607A (en) 1989-05-30 1989-05-30 High speed photopolymerizable element with initiator in a topcoat
CA002015852A CA2015852A1 (fr) 1989-05-30 1990-05-01 Cliche d'impression a photopolymerisation rapide avec agent d'amorcage dans la surcouche
EP90305728A EP0403096B1 (fr) 1989-05-30 1990-05-25 Plaque d'impression photopolymérisable à grande vitesse avec initiateur dans la couche de protection
DE69028044T DE69028044T2 (de) 1989-05-30 1990-05-25 Hochgeschwindige, photopolymerisierbare Druckplatte mit einem Initiator in der Deckschicht
KR1019900007742A KR910020499A (ko) 1989-05-30 1990-05-29 상부 피복에 개시제를 함유한 고속 광중합성 프린트 플레이트
JP2139563A JPH0329948A (ja) 1989-05-30 1990-05-29 上層に開始剤を含有する高速度光重合性印刷版

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US07/357,908 US4988607A (en) 1989-05-30 1989-05-30 High speed photopolymerizable element with initiator in a topcoat

Publications (1)

Publication Number Publication Date
US4988607A true US4988607A (en) 1991-01-29

Family

ID=23407523

Family Applications (1)

Application Number Title Priority Date Filing Date
US07/357,908 Expired - Lifetime US4988607A (en) 1989-05-30 1989-05-30 High speed photopolymerizable element with initiator in a topcoat

Country Status (6)

Country Link
US (1) US4988607A (fr)
EP (1) EP0403096B1 (fr)
JP (1) JPH0329948A (fr)
KR (1) KR910020499A (fr)
CA (1) CA2015852A1 (fr)
DE (1) DE69028044T2 (fr)

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5273862A (en) * 1988-07-29 1993-12-28 Hoechst Aktiengesellschaft Photopolymerizable recording material comprising a cover layer substantially impermeable to oxygen, binds oxygen and is soluble in water at 20°C.
US5300536A (en) * 1989-10-06 1994-04-05 Toagosei Chemical Industry Co., Ltd. Catalytic composition for photopolymerization and a photopolymerizable composition containing the same
US5395862A (en) * 1992-12-09 1995-03-07 Spectra Group Limited, Inc. Photooxidizable initiator composition and photosensitive materials containing the same
US5639802A (en) * 1991-05-20 1997-06-17 Spectra Group Limited, Inc. Cationic polymerization
US5821030A (en) * 1995-07-20 1998-10-13 Kodak Polychrome Graphics Lithographic printing plates having a photopolymerizable imaging layer overcoated with an oxygen barrier layer
US5973020A (en) * 1998-01-06 1999-10-26 Rhodia Inc. Photoinitiator composition including hindered amine stabilizer
US5981146A (en) * 1992-05-25 1999-11-09 Mitsubishi Denki Kabushiki Kaisha Resist coating film
WO2000042080A1 (fr) * 1999-01-15 2000-07-20 The Curators Of The University Of Missouri Formulations de monomeres a base d'ether vinylique photopolymerisable et compositions polymerisables pouvant comprendre certains nouveaux spiro-ortho-carbonates
US6171759B1 (en) * 1992-05-14 2001-01-09 Brother Kogyo Kabushiki Kaisha Photocurable composition
US6218445B1 (en) * 1996-08-21 2001-04-17 Rhodia Chimie Stable polyorganosiloxane based compositions with cross-linkable functional groups and their use for producing antiadhesive coating
US6537309B2 (en) * 2001-03-26 2003-03-25 Council Of Scientific And Industrial Research Reusable heat pack, method of manufacture thereof, mixture for use in a reusable heatpack and process for the preparation thereof
US6610759B1 (en) 2000-03-06 2003-08-26 Curators Of The University Of Missouri Cationically polymerizable adhesive composition containing an acidic component and methods and materials employing same
US20030190491A1 (en) * 2002-04-04 2003-10-09 3M Innovative Properties Company K-type polarizer and preparation thereof
US20030189264A1 (en) * 2002-04-04 2003-10-09 3M Innovative Properties Company K-type polarizer and preparation thereof
US20100009292A1 (en) * 2007-02-26 2010-01-14 Jsr Corporation Resin composition for micropattern formation and method of micropattern formation

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0465034B1 (fr) * 1990-06-18 1996-08-14 Nippon Paint Co., Ltd. Composition de résine photosensible pour l'impression flexographique
US5254437A (en) * 1990-06-18 1993-10-19 Nippon Paint Co., Ltd. Photosensitive resin composition for flexographic printing
DE10022786B4 (de) 1999-05-12 2008-04-10 Kodak Graphic Communications Gmbh Auf der Druckmaschine entwickelbare Druckplatte
EP2194429A1 (fr) 2008-12-02 2010-06-09 Eastman Kodak Company Compositions de gommage avec nanoparticules pour l'amélioration de la sensibilité aux éraflures et des zones sans images des plaques d'impression lithographiques
EP2196851A1 (fr) 2008-12-12 2010-06-16 Eastman Kodak Company Précurseurs de plaque d'impression lithographique à action négative comportant une liaison réactive contenant des caractéristiques aliphatiques bi ou polycycliques
US8034538B2 (en) 2009-02-13 2011-10-11 Eastman Kodak Company Negative-working imageable elements
US20100215919A1 (en) 2009-02-20 2010-08-26 Ting Tao On-press developable imageable elements
US8247163B2 (en) 2009-06-12 2012-08-21 Eastman Kodak Company Preparing lithographic printing plates with enhanced contrast
US8257907B2 (en) 2009-06-12 2012-09-04 Eastman Kodak Company Negative-working imageable elements
EP2284005B1 (fr) 2009-08-10 2012-05-02 Eastman Kodak Company Précurseurs de plaque d'impression lithographique dotés d'agents de réticulation à base de bêta-hydroxyalkylamide
EP2293144B1 (fr) 2009-09-04 2012-11-07 Eastman Kodak Company Procédé pour le séchage de plaques d'impression lithographique consécutif à un processus à étape unique
EP2735903B1 (fr) 2012-11-22 2019-02-27 Eastman Kodak Company Précurseurs de plaque d'impression lithographique au travail négative comprenant une matière liante hyper-ramifié
EP2778782B1 (fr) 2013-03-13 2015-12-30 Kodak Graphic Communications GmbH Éléments sensibles au rayonnement à travail négatif
AT527021B1 (de) * 2023-02-28 2025-04-15 Univ Wien Tech Photobasen

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4250053A (en) * 1979-05-21 1981-02-10 Minnesota Mining And Manufacturing Company Sensitized aromatic iodonium or aromatic sulfonium salt photoinitiator systems
US4332873A (en) * 1979-08-22 1982-06-01 Hercules Incorporated Multilayer printing plates and process for making same
US4366218A (en) * 1981-07-13 1982-12-28 Eastman Kodak Company Photographic products and processes employing novel nondiffusible bridged azdaminophenol magenta dye-releasing compounds and precursors thereof
US4599299A (en) * 1982-04-22 1986-07-08 E. I. Du Pont De Nemours And Company Process for preparing overcoated photohardenable element having surface protuberances

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2011100B (en) * 1977-12-21 1982-05-26 Letraset International Ltd Production of transfer materials
DE2923980A1 (de) * 1978-06-14 1980-01-03 Polychrome Corp Mehrschichtfolie zur herstellung eines positivs und eines negativs von einem transparentbild
CA1323949C (fr) * 1987-04-02 1993-11-02 Michael C. Palazzotto Systeme ternaire de photoinitiateur pour la polymerisation additive

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4250053A (en) * 1979-05-21 1981-02-10 Minnesota Mining And Manufacturing Company Sensitized aromatic iodonium or aromatic sulfonium salt photoinitiator systems
US4332873A (en) * 1979-08-22 1982-06-01 Hercules Incorporated Multilayer printing plates and process for making same
US4366218A (en) * 1981-07-13 1982-12-28 Eastman Kodak Company Photographic products and processes employing novel nondiffusible bridged azdaminophenol magenta dye-releasing compounds and precursors thereof
US4599299A (en) * 1982-04-22 1986-07-08 E. I. Du Pont De Nemours And Company Process for preparing overcoated photohardenable element having surface protuberances

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5273862A (en) * 1988-07-29 1993-12-28 Hoechst Aktiengesellschaft Photopolymerizable recording material comprising a cover layer substantially impermeable to oxygen, binds oxygen and is soluble in water at 20°C.
US5300536A (en) * 1989-10-06 1994-04-05 Toagosei Chemical Industry Co., Ltd. Catalytic composition for photopolymerization and a photopolymerizable composition containing the same
US5639802A (en) * 1991-05-20 1997-06-17 Spectra Group Limited, Inc. Cationic polymerization
US6171759B1 (en) * 1992-05-14 2001-01-09 Brother Kogyo Kabushiki Kaisha Photocurable composition
US5981146A (en) * 1992-05-25 1999-11-09 Mitsubishi Denki Kabushiki Kaisha Resist coating film
US5395862A (en) * 1992-12-09 1995-03-07 Spectra Group Limited, Inc. Photooxidizable initiator composition and photosensitive materials containing the same
US5821030A (en) * 1995-07-20 1998-10-13 Kodak Polychrome Graphics Lithographic printing plates having a photopolymerizable imaging layer overcoated with an oxygen barrier layer
US5888700A (en) * 1995-07-20 1999-03-30 Kodak Polychrome Grpahics, Llc Lithographic printing plates having a photopolymerizable imaging layer overcoated with an oxygen barrier layer
US6218445B1 (en) * 1996-08-21 2001-04-17 Rhodia Chimie Stable polyorganosiloxane based compositions with cross-linkable functional groups and their use for producing antiadhesive coating
US5973020A (en) * 1998-01-06 1999-10-26 Rhodia Inc. Photoinitiator composition including hindered amine stabilizer
WO2000042080A1 (fr) * 1999-01-15 2000-07-20 The Curators Of The University Of Missouri Formulations de monomeres a base d'ether vinylique photopolymerisable et compositions polymerisables pouvant comprendre certains nouveaux spiro-ortho-carbonates
US6458865B2 (en) 1999-01-15 2002-10-01 Curators Of The University Of Missouri Photopolymerizable vinyl ether based monomeric formulations and polymerizable compositions which may include certain novel spiroorthocarbonates
US6653486B2 (en) * 1999-01-15 2003-11-25 Curators Of The University Of Missouri Spiroorthocarbonates containing epoxy groups
US6610759B1 (en) 2000-03-06 2003-08-26 Curators Of The University Of Missouri Cationically polymerizable adhesive composition containing an acidic component and methods and materials employing same
US6537309B2 (en) * 2001-03-26 2003-03-25 Council Of Scientific And Industrial Research Reusable heat pack, method of manufacture thereof, mixture for use in a reusable heatpack and process for the preparation thereof
US20030190491A1 (en) * 2002-04-04 2003-10-09 3M Innovative Properties Company K-type polarizer and preparation thereof
US20030189264A1 (en) * 2002-04-04 2003-10-09 3M Innovative Properties Company K-type polarizer and preparation thereof
US6949207B2 (en) 2002-04-04 2005-09-27 3M Innovative Properties Company K-type polarizer and preparation thereof
US7087194B2 (en) 2002-04-04 2006-08-08 3M Innovative Properties Company K-type polarizer and preparation thereof
US20100009292A1 (en) * 2007-02-26 2010-01-14 Jsr Corporation Resin composition for micropattern formation and method of micropattern formation

Also Published As

Publication number Publication date
DE69028044D1 (de) 1996-09-19
EP0403096A3 (fr) 1991-11-21
EP0403096B1 (fr) 1996-08-14
EP0403096A2 (fr) 1990-12-19
CA2015852A1 (fr) 1990-11-30
KR910020499A (ko) 1991-12-20
DE69028044T2 (de) 1997-03-06
JPH0329948A (ja) 1991-02-07

Similar Documents

Publication Publication Date Title
US4988607A (en) High speed photopolymerizable element with initiator in a topcoat
US4282309A (en) Photosensitive composition containing an ethylenically unsaturated compound, initiator and sensitizer
US4239850A (en) Photopolymerizable composition
EP0107792B1 (fr) Compositions photopolymérisables
JP3365434B2 (ja) 光重合性組成物及び感光材料
US4258123A (en) Photosensitive resin composition
US4971892A (en) High sensitivity photopolymerizable composition
JPH0629285B2 (ja) 光重合性組成物
JPH01152109A (ja) 光重合性組成物
AU603235B2 (en) Photopolymerizable composition
JP3118520B2 (ja) 光重合性記録材料の造像的照射による印刷板またはフォトレジストの製法
JPS5819315A (ja) 光重合性組成物
JPH0743896A (ja) 光重合性組成物
JPH0635189A (ja) 光重合性混合物およびそれから調製される記録材料
JPH0255446B2 (fr)
US4990428A (en) Photosensitive planographic printing plate
JP3220498B2 (ja) 光重合性組成物
US5837586A (en) 4-(alkoxyhydroxy)styryl triazine photinitiators and photo sensitive composition
JPH05241338A (ja) 光重合性組成物
JPH02151606A (ja) 光重合性混合物及びそれから製造される記録材料
JPH0588243B2 (fr)
US4945027A (en) 1,4 or 9,10 dimethoxyanthracene triggers for 2-tri(chloro or bromo)methyl-4(1H)-quinazolimone polymerization initiators
JPH0588244B2 (fr)
JPH08297367A (ja) 光重合性組成物
JPH08114915A (ja) 光重合性組成物

Legal Events

Date Code Title Description
AS Assignment

Owner name: MINNESOTA MINING AND MANUFACTURING COMPANY, SAINT

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:ALI, MOHAMMAD Z.;REEL/FRAME:005086/0848

Effective date: 19890524

STCF Information on status: patent grant

Free format text: PATENTED CASE

CC Certificate of correction
FPAY Fee payment

Year of fee payment: 4

FPAY Fee payment

Year of fee payment: 8

FPAY Fee payment

Year of fee payment: 12